N-(2-furylcarbonyl)piperidine-1-carbothioamide

The title compound, C11H14N2O2S, was synthesized from furoyl isothiocyanate and piperidine in dry acetone. The thiourea group is in the thioamide form. The thiourea group makes a dihedral angle of 53.9 (1)degrees with the furan carbonyl group. In the crystal structure, molecules are linked by intermolecular N-H center dot center dot center dot O hydrogen bonds, forming one-dimensional chains along the c axis. An intramolecular N-H center dot center dot center dot O hydrogen bond is also present.

Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

1-(2-furoyl)-3-(1-naphthyl)thiourea

In the title compound, C(16)H(12)N(2)O(2)S, the carbonylthiourea group forms dihedral angles of 75.4 (1) and 13.1 (2)degrees, respectively, with the naphthalene ring system and furan ring. The molecule adopts a trans-cis configuration with respect to the positions of the furoyl and naphthyl groups relative to the S atom across the thiourea C-N bonds. This geometry is stabilized by an N-H center dot center dot center dot center dot O intramolecular hydrogen bond. In the crystal structure, molecules are linked by N-H center dot center dot center dot S hydrogen bonds, forming centrosymmetric dimers which are interlinked through C-H center dot center dot center dot pi interactions.

Transition-metal 13-atom clusters assessed with solid and surface-biased functionals

First-principles density-functional theory studies have reported open structures based on the formation of double simple-cubic (DSC) arrangements for Ru(13), Rh(13), Os(13), and Ir(13), which can be considered an unexpected result as those elements crystallize in compact bulk structures such as the face-centered cubic and hexagonal close-packed lattices. In this work, we investigated with the projected augmented wave method the dependence of the lowest-energy structure on the local and semilocal exchange-correlation (xc) energy functionals employed in density-functional theory. We found that the local-density approximation (LDA) and generalized-gradient formulations with different treatment of the electronic inhomogeneities (PBE, PBEsol, and AM05) confirm the DSC configuration as the lowest-energy structure for the studied TM(13) clusters. A good agreement in the relative total energies are obtained even for structures with small energy differences, e. g., 0.10 eV. The employed xc functionals yield the same total magnetic moment for a given structure, i.e., the differences in the bond lengths do not affect the moments, which can be attributed to the atomic character of those clusters. Thus, at least for those systems, the differences among the LDA, PBE, PBEsol, and AM05 functionals are not large enough to yield qualitatively different results. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3577999]

5-Methyl-2,4-bis(methylsulfanyl)tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-3,6-dione

The structure analysis of the title compound, C(14)H(16)O(2)S(2), shows the SMe and H atoms of the bond linking the six-membered rings to be syn and also to be syn to the bridgehead -CH(2)- group. Each of the five-membered rings adopts an envelope conformation at the bridgehead -CH(2)- group. The dione-substituted ring adopts a folded conformation about the 1,4-C center dot center dot center dot C vector, with the ketone groups lying to one side. The cyclohexene ring adopts a boat conformation.

Knoop Microhardness and FT-Raman Spectroscopic Evaluation of a Resin-Based Dental Material Light-Cured by an Argon Ion Laser and Halogen Lamp: An in Vitro Study

Objective: The purpose of this study was to evaluate in vitro the Knoop microhardness (Knoop hardness number [KHN]) and the degree of conversion using FT-Raman spectroscopy of a light-cured microhybrid resin composite (Z350-3M-ESPE) Vita shade A3 photopolymerized with a halogen lamp or an argon ion laser. Background Data: Optimal polymerization of resin-based dental materials is important for longevity of restorations in dentistry. Materials and Methods: Thirty specimens were prepared and inserted into a disc-shaped polytetrafluoroethylene mold that was 2.0 mm thick and 3 mm in diameter. The specimens were divided into three groups (n = 10 each). Group 1 (G1) was light-cured for 20 sec with an Optilux 501 halogen light with an intensity of 1000 mW/cm(2). Group 2 (G2) was photopolymerized with an argon laser with a power of 150 mW for 10 sec, and group 3 (G3) was photopolymerized with an argon laser at 200 mW of power for 10 sec. All specimens were stored in distilled water for 24 h at 37 degrees C and kept in lightproof containers. For the KHN test five indentations were made and a depth of 100 mu m was maintained in each specimen. One hundred and fifty readings were obtained using a 25-g load for 45 sec. The degree of conversion values were measured by Raman spectroscopy. KHN and degree of conversion values were obtained on opposite sides of the irradiated surface. KHN and degree of conversion data were analyzed by one-way ANOVA and Tukey tests with statistical significance set at p < 0.05. Results: The results of KHN testing were G1 = 37.428 +/- 4.765; G2 = 23.588 +/- 6.269; and G3 = 21.652 +/- 4.393. The calculated degrees of conversion (DC%) were G1 = 48.57 +/- 2.11; G2 = 43.71 +/- 3.93; and G3 = 44.19 +/- 2.71. Conclusions: Polymerization with the halogen lamp ( G1) attained higher microhardness values than polymerization with the argon laser at power levels of 150 and 200 mW; there was no difference in hardness between the two argon laser groups. The results showed no statistically significant different degrees of conversion for the polymerization of composite samples with the two light sources tested.

In situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction

Early reports stated that Au was a catalyst of choice for the BOR because it would yield a near complete faradaic efficiency. However, it has recently been suggested that gold could yield to some extent the heterogeneous hydrolysis of BH(4)(-),therefore lowering the electron count per BH(4)(-), especially at low potential. Actually, the blur will exist regarding the BOR mechanism on Au as long as no physical proof regarding the reaction intermediates is not put forward. In that frame, in situ physical techniques like FTIR exhibit some interest to study the BOR. Consequently, in situ infrared reflectance spectroscopy measurements (SPAIRS technique) have been performed in 1 M NaOH/1 M NaBH(4) on a gold electrode with the aim to detect the intermediate species. We monitored several bands in B-H ((nu) over bar similar to 1180,1080 and 972 cm(-1)) and B-O bond regions ((nu) over bar =1325 and similar to 1425cm(-1)), which appear sequentially as a function of the electrode polarization. These absorption bands are assigned to BH(3), BH(2) and BO(2)(-) species. At the light of the experimental results, possible initial elementary steps of the BOR on gold electrode have been proposed and discussed according to the relevant literature data.

Catalytic oxidation of ethanol on gold electrode in alkaline media

This work presents a study of the catalytic oxidation of ethanol on polycrystalline gold electrode in alkaline media. The investigation was carried out by means of chronoamperometry, cyclic voltammetry, and in situ FTIR spectroscopy. The main goal was to investigate the early stages of ethanol electrooxidation, namely at fairly low potentials (E = 600 mV vs. RHE) and for moderate reaction times (t < 300 s). Chronoamperometric experiments show a current increase accompanying the increasing in the ethanol concentration up to about 2 M and then a slight decrease at 3 M. Adsorbed CO has been observed as early as about 200 mV vs. RHE and indicates that the cleavage of the C-C bond might occur, probably to a small extent, at very low overpotentials during ethanol adsorption on gold surface. The amount of dissolved acetate ions produced during the chronoamperomentry was followed by the asymmetric stretching band at 1558 cm(-1) as a function of time, and found to increase linearly with time up to 300 s. This allowed estimating the reaction order of acetate formation with respect to ethanol concentration.

Surface structure effects on the electrochemical oxidation of ethanol on platinum single crystal electrodes

Ethanol oxidation has been studied on Pt(111), Pt(100) and Pt(110) electrodes in order to investigate the effect of the surface structure and adsorbing anions using electrochemical and FTIR techniques. The results indicate that the surface structure and anion adsorption affect significantly the reactivity of the electrode. Thus, the main product of the oxidation of ethanol on the Pt(111) electrode is acetic acid, and acetaldehyde is formed as secondary product. Moreover, the amount of CO formed is very small, and probably associated with the defects present on the electrode surface. For that reason, the amount of CO(2) is also small. This electrode has the highest catalytic activity for the formation of acetic acid in perchloric acid. However, the formation of acetic acid is inhibited by the presence of specifically adsorbed anions, such as (bi) sulfate or acetate, which is the result of the formation of acetic acid. On the other hand, CO is readily formed at low potentials on the Pt(100) electrode, blocking completely the surface. Between 0.65 and 0.80 V, the CO layer is oxidized and the production of acetaldehyde and acetic acid is detected. The Pt(110) electrode displays the highest catalytic activity for the splitting of the C-C bond. Reactions giving rise to CO formation, from either ethanol or acetaldehyde, occur at high rate at any potential. On the other hand, the oxidation of acetaldehyde to acetic acid has probably the lower reaction rate of the three basal planes.

Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies

Oxidation of ethanol on ruthenium-modified Pt(775) and Pt(332) stepped electrodes has been studied using electrochemical and FTIR techniques. It has been found that the oxidation of ethanol on these electrodes takes place preferentially on the step sites yielding CO(2) as the major final product. The cleavage of the C-C bond, which is the required step to yield CO(2), occurs only on this type of site. The presence of low ruthenium coverages on the step sites promotes the complete oxidation of ethanol since it facilitates the oxidation of CO formed on the step from the cleavage of the C-C bond. However, high ruthenium coverages have an important inhibiting effect since the adatoms block the step sites, which are required for the cleavage of the C-C bond. Under these conditions, the oxidation current diminishes and the major product in the oxidation process is acetic acid, which is the product formed preferentially on the (111) terrace sites.

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.

Effect of Oxalate Desensitizer on the Durability of Resin-Bonded Interfaces

Potassium oxalate desensitizers were previously shown to effectively reduce the immediate permeability of resin-bonded dentin. The current study evaluated whether the effect of the combined application of oxalate with etch-and-rinse adhesives interferes with the durability of resin-dentin bonds when using etch-and-rinse adhesives. The bond strength of resin-bonded dentin specimens composed of two-step or three-step etch-and-rinse adhesives (Single Bond, One-Step and Scotchbond Multi-Purpose, respectively) was tested immediately (24 hours) and after 12 months of water storage. The adhesives were used either according to the manufacturers` instructions (control groups) or after treating acid-etched dentin with a potassium oxalate gel (BisBlock, BISCO, Inc). The treatment of dentin with potassium oxalate was shown to negatively affect the baseline bond strength of resin-bonded dentin specimens, regardless of the adhesive used (p<0.05). After storage, the bond strength of the resin-bonded interfaces was significantly reduced for all the tested groups (p<0.001). Nevertheless, the rate of decreasing bond strength was significantly lower for oxalate-treated specimens than for the controls (p<0.05).

Cellulose modified fibres in cement based composites

The objective of the present work is to evaluate the effect of surface modification of cellulose pulp fibres on the mechanical and microstructure of fibre-cement composites. Surface modification of the cellulose pulps was performed with Methacryloxypropyltri-methoxysilane (MPTS) and Aminopropyltri-ethoxysilane (APTS) in an attempt to improve their durability into fibre-cement composites. The surface modification showed significant influence on the microstructure of the composites on the fibre-matrix interface and in the mineralization of the fibre lumen as seen by scanning electron microscopy (SEM) with back-scattered electron (BSE) detector. Accelerated ageing cycles decreased modulus of rupture (MOR) and toughness (TE) of the composites. Composites reinforced with MPTS-modified fibres presented fibres free from cement hydration products, while APTS-modified fibres presented accelerated mineralization. Higher mineralization of the fibres led to higher embrittlement of the composite after accelerated ageing cycles. These observations are therefore very useful for understanding the mechanisms of degradation of fibre-cement composites. (C) 2009 Elsevier Ltd. All rights reserved.

Predicting glass-forming compositions in the Al-La and Al-La-Ni systems

In this work, a criterion considering the topological instability (lambda) and the differences in the electronegativity of the constituent elements (Delta e) was applied to the Al-La and Al-Ni-La systems in order to predict the best glass-forming compositions. The results were compared with literature data and with our own experimental data for the Al-La-Ni system. The alloy described in the literature as the best glass former in the Al-La system is located near the point with local maximum for the lambda.Delta e criterion. A good agreement was found between the predictions of the lambda.Delta e criterion and literature data in the Al-La-Ni system, with the region of the best glass-forming ability (GFA) and largest supercooled liquid region (Delta T(x)) coinciding with the best compositional region for amorphization indicated by the lambda.Delta e criterion. Four new glassy compositions were found in the Al-La-Ni system, with the best predicted composition presenting the best glass-forming ability observed so far for this system. Although the lambda.Delta e criterion needs further refinements for completely describe the glass-forming ability in the Al-La and Al-La-Ni systems, the results demonstrated that this criterion is a good tool to predict new glass-forming compositions. (C) 2010 Elsevier B. V. All rights reserved.

Influence of EVA and acrylate polymers on some mechanical properties of cementitious repair mortars

In repair works of reinforced concrete, patch repairs tend to crack in the interfacial zone between the mortar and the old concrete. This occurs basically due to the high degree of restriction that acts on a patch repair. For this reason, the technology of patch repair needs to be the subject of a discussion involving professionals who work with projects, construction maintenance and mix proportioning of repair mortars. In the present work, a study is presented on the benefits that the ethylene vinyl acetate copolymer (EVA) and acrylate polymers can provide in the mix proportioning of a repair mortar with respect to compressive, tensile and direct-shear bond strength. The results indicated that the increase in bond strength and the reduction in the influence of the deficiency in Curing conditioning are the main contributions offered by the polymers studied here. (C) 2009 Elsevier, Ltd. All rights reserved.